The structure of the title compound, [V(C5H5)2Cl(C2H3N)][FeCl4], a potential spermicidally active species, has been determined. This compound has a typical bent metallocene structure, in which two η5-bonded cyclopentadienyl rings, an N-coordinated acetonitrile molecule and a Cl ligand occupy tetrahedral positions around the VIV atom. The V—N bond length was found to be 2.087 (2) Å.
Supporting information
CCDC reference: 262272
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.022
- wR factor = 0.054
- Data-to-parameter ratio = 21.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) V1 - N1 .. 5.32 su
| Author Response: :
The anisotropic displacement parameters of nitrogen in acetonitrile moiety
are affected by large deviations of its electron density from approximation
of independent atom model due delocalization into multiple
bonds system. Therefore the refinement of parameters of either anharmonic
thermal motion or atom asphericity would probably solve the problem, however
it is behind the scope of this experiment.
|
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Fe1
| Author Response: :
Probably false alarm as Fe is in the centre of gravity of isolated FeCl4
moiety,
serving as pivot atom for the most displacements.
|
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.49
From the CIF: _reflns_number_total 3946
Count of symmetry unique reflns 2269
Completeness (_total/calc) 173.91%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1677
Fraction of Friedel pairs measured 0.739
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Acetonitrilechlorobis(
η5-cyclopentadienyl)vanadium(IV) tetrachloroiron(III)
top
Crystal data top
[V(C5H5)2Cl(C2H3N)][FeCl4] | F(000) = 904 |
Mr = 455.27 | Dx = 1.756 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 27318 reflections |
a = 7.3730 (2) Å | θ = 1–27.5° |
b = 13.5290 (3) Å | µ = 2.15 mm−1 |
c = 17.2680 (3) Å | T = 150 K |
V = 1722.47 (7) Å3 | Plate, green |
Z = 4 | 0.5 × 0.42 × 0.18 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3946 independent reflections |
Radiation source: fine-focus sealed tube | 3789 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 1.9° |
φ and ω scans to fill the Ewald sphere | h = −9→9 |
Absorption correction: integration Gaussian (Coppens & Hamilton, 1970) | k = −17→17 |
Tmin = 0.405, Tmax = 0.712 | l = −22→22 |
26509 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0261P)2 + 0.6271P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3946 reflections | Δρmax = 0.29 e Å−3 |
185 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.003 (13) |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
V1 | 0.63054 (4) | 0.95681 (2) | 0.552522 (17) | 0.01552 (7) | |
C1 | 0.9281 (3) | 0.90703 (15) | 0.53904 (12) | 0.0253 (4) | |
H1 | 0.9857 | 0.8654 | 0.5742 | 0.030* | |
C2 | 0.8295 (3) | 0.87676 (17) | 0.47408 (12) | 0.0262 (4) | |
H2 | 0.8066 | 0.8118 | 0.4595 | 0.031* | |
C3 | 0.7713 (3) | 0.9618 (2) | 0.43487 (12) | 0.0360 (5) | |
H3 | 0.7056 | 0.9631 | 0.3889 | 0.043* | |
C4 | 0.8291 (3) | 1.04389 (17) | 0.47678 (15) | 0.0386 (6) | |
H4 | 0.8079 | 1.1096 | 0.4639 | 0.046* | |
C5 | 0.9257 (3) | 1.00999 (16) | 0.54230 (14) | 0.0328 (5) | |
H5 | 0.9781 | 1.0491 | 0.5805 | 0.039* | |
C6 | 0.5342 (3) | 1.00632 (15) | 0.67307 (12) | 0.0278 (5) | |
H6 | 0.5588 | 0.9701 | 0.7176 | 0.033* | |
C7 | 0.3831 (3) | 0.99371 (16) | 0.62469 (12) | 0.0286 (4) | |
H7 | 0.2919 | 0.9468 | 0.6308 | 0.034* | |
C8 | 0.3939 (3) | 1.06489 (16) | 0.56501 (12) | 0.0305 (4) | |
H8 | 0.3104 | 1.0739 | 0.5253 | 0.037* | |
C9 | 0.5520 (3) | 1.11912 (15) | 0.57638 (13) | 0.0304 (5) | |
H9 | 0.5923 | 1.1709 | 0.5454 | 0.037* | |
C10 | 0.6416 (3) | 1.08242 (15) | 0.64301 (12) | 0.0283 (4) | |
H10 | 0.7513 | 1.1047 | 0.6630 | 0.034* | |
N1 | 0.6402 (2) | 0.82581 (12) | 0.61624 (9) | 0.0228 (3) | |
C11 | 0.6483 (3) | 0.75386 (15) | 0.65019 (11) | 0.0246 (4) | |
C12 | 0.6593 (3) | 0.66295 (17) | 0.69448 (14) | 0.0336 (5) | |
H12D | 0.5947 | 0.6707 | 0.7424 | 0.057 (18)* | 0.50 |
H12E | 0.7841 | 0.6480 | 0.7051 | 0.024 (12)* | 0.50 |
H12F | 0.6063 | 0.6099 | 0.6652 | 0.045 (15)* | 0.50 |
H12A | 0.7560 | 0.6228 | 0.6746 | 0.067* | 0.50 |
H12B | 0.5467 | 0.6277 | 0.6902 | 0.067* | 0.50 |
H12C | 0.6823 | 0.6782 | 0.7479 | 0.067* | 0.50 |
Cl1 | 0.40993 (8) | 0.87440 (4) | 0.47654 (3) | 0.03139 (12) | |
Fe1 | 0.11245 (4) | 0.83620 (2) | 0.798789 (15) | 0.02197 (7) | |
Cl2 | 0.16516 (8) | 0.74293 (4) | 0.69784 (3) | 0.03340 (12) | |
Cl3 | −0.01846 (8) | 0.97165 (4) | 0.75778 (3) | 0.03372 (13) | |
Cl4 | −0.06343 (10) | 0.75477 (4) | 0.87977 (4) | 0.04391 (16) | |
Cl5 | 0.36852 (11) | 0.87179 (5) | 0.85517 (4) | 0.05383 (19) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.01477 (14) | 0.01510 (13) | 0.01669 (14) | 0.00005 (12) | 0.00139 (12) | −0.00017 (11) |
C1 | 0.0146 (9) | 0.0327 (10) | 0.0285 (10) | 0.0049 (8) | 0.0037 (8) | 0.0047 (8) |
C2 | 0.0230 (10) | 0.0305 (11) | 0.0250 (10) | 0.0038 (8) | 0.0085 (8) | −0.0065 (8) |
C3 | 0.0267 (11) | 0.0595 (15) | 0.0217 (10) | 0.0093 (11) | 0.0086 (8) | 0.0127 (10) |
C4 | 0.0307 (12) | 0.0271 (11) | 0.0578 (15) | 0.0064 (9) | 0.0273 (11) | 0.0164 (10) |
C5 | 0.0173 (10) | 0.0352 (11) | 0.0459 (13) | −0.0077 (8) | 0.0087 (9) | −0.0097 (10) |
C6 | 0.0354 (12) | 0.0285 (11) | 0.0194 (9) | 0.0051 (9) | 0.0067 (8) | −0.0036 (8) |
C7 | 0.0199 (10) | 0.0320 (11) | 0.0341 (11) | 0.0009 (9) | 0.0100 (9) | −0.0063 (8) |
C8 | 0.0247 (10) | 0.0324 (11) | 0.0343 (11) | 0.0151 (9) | 0.0005 (9) | −0.0037 (9) |
C9 | 0.0397 (13) | 0.0170 (9) | 0.0347 (11) | 0.0054 (9) | 0.0088 (9) | −0.0012 (8) |
C10 | 0.0283 (11) | 0.0263 (10) | 0.0302 (10) | 0.0002 (9) | 0.0024 (9) | −0.0131 (8) |
N1 | 0.0245 (9) | 0.0218 (8) | 0.0221 (7) | 0.0009 (7) | 0.0037 (7) | 0.0022 (6) |
C11 | 0.0224 (10) | 0.0269 (10) | 0.0244 (9) | 0.0006 (8) | 0.0022 (8) | 0.0012 (8) |
C12 | 0.0361 (12) | 0.0278 (11) | 0.0369 (11) | 0.0007 (10) | 0.0031 (10) | 0.0138 (10) |
Cl1 | 0.0301 (3) | 0.0320 (3) | 0.0321 (3) | −0.0069 (2) | −0.0083 (2) | −0.0054 (2) |
Fe1 | 0.02673 (15) | 0.02026 (13) | 0.01892 (13) | −0.00017 (12) | −0.00264 (11) | −0.00072 (10) |
Cl2 | 0.0450 (3) | 0.0294 (3) | 0.0258 (2) | 0.0052 (2) | 0.0044 (2) | −0.0062 (2) |
Cl3 | 0.0427 (3) | 0.0287 (3) | 0.0297 (3) | 0.0115 (2) | −0.0006 (2) | 0.0018 (2) |
Cl4 | 0.0588 (4) | 0.0317 (3) | 0.0412 (3) | 0.0015 (3) | 0.0238 (3) | 0.0056 (2) |
Cl5 | 0.0522 (4) | 0.0472 (4) | 0.0620 (4) | −0.0133 (3) | −0.0364 (4) | 0.0083 (3) |
Geometric parameters (Å, º) top
Cg1—V1 | 1.956 (1) | C5—H5 | 0.9300 |
Cg2—V1 | 1.958 (1) | C6—C10 | 1.399 (3) |
V1—N1 | 2.0873 (16) | C6—C7 | 1.403 (3) |
V1—C7 | 2.265 (2) | C6—H6 | 0.9300 |
V1—C2 | 2.272 (2) | C7—C8 | 1.413 (3) |
V1—C3 | 2.283 (2) | C7—H7 | 0.9300 |
V1—C8 | 2.286 (2) | C8—C9 | 1.391 (3) |
V1—C4 | 2.290 (2) | C8—H8 | 0.9300 |
V1—C6 | 2.2991 (19) | C9—C10 | 1.417 (3) |
V1—C5 | 2.299 (2) | C9—H9 | 0.9300 |
V1—C1 | 2.3070 (19) | C10—H10 | 0.9300 |
V1—C9 | 2.308 (2) | N1—C11 | 1.138 (3) |
V1—C10 | 2.3101 (19) | C11—C12 | 1.451 (3) |
V1—Cl1 | 2.3685 (6) | C12—H12D | 0.9600 |
C1—C5 | 1.394 (3) | C12—H12E | 0.9600 |
C1—C2 | 1.398 (3) | C12—H12F | 0.9600 |
C1—H1 | 0.9300 | C12—H12A | 0.9600 |
C2—C3 | 1.402 (3) | C12—H12B | 0.9600 |
C2—H2 | 0.9300 | C12—H12C | 0.9600 |
C3—C4 | 1.392 (4) | Fe1—Cl5 | 2.1781 (7) |
C3—H3 | 0.9300 | Fe1—Cl2 | 2.1867 (6) |
C4—C5 | 1.413 (4) | Fe1—Cl3 | 2.1889 (6) |
C4—H4 | 0.9300 | Fe1—Cl4 | 2.2025 (6) |
| | | |
Cg1—V1—Cg2 | 134.10 (4) | V1—C1—H1 | 123.0 |
N1—V1—C7 | 85.68 (7) | C1—C2—C3 | 107.8 (2) |
N1—V1—C2 | 83.54 (7) | C1—C2—V1 | 73.61 (11) |
C7—V1—C2 | 162.43 (8) | C3—C2—V1 | 72.49 (12) |
N1—V1—C3 | 118.61 (8) | C1—C2—H2 | 126.1 |
C7—V1—C3 | 148.15 (8) | C3—C2—H2 | 126.1 |
C2—V1—C3 | 35.86 (8) | V1—C2—H2 | 119.7 |
N1—V1—C8 | 121.29 (8) | C4—C3—C2 | 108.0 (2) |
C7—V1—C8 | 36.16 (8) | C4—C3—V1 | 72.55 (12) |
C2—V1—C8 | 148.64 (8) | C2—C3—V1 | 71.64 (11) |
C3—V1—C8 | 114.33 (8) | C4—C3—H3 | 126.0 |
N1—V1—C4 | 135.74 (8) | C2—C3—H3 | 126.0 |
C7—V1—C4 | 135.72 (8) | V1—C3—H3 | 121.6 |
C2—V1—C4 | 59.45 (8) | C3—C4—C5 | 108.15 (19) |
C3—V1—C4 | 35.46 (10) | C3—C4—V1 | 71.99 (12) |
C8—V1—C4 | 102.28 (8) | C5—C4—V1 | 72.43 (12) |
N1—V1—C6 | 77.33 (7) | C3—C4—H4 | 125.9 |
C7—V1—C6 | 35.80 (8) | C5—C4—H4 | 125.9 |
C2—V1—C6 | 151.44 (8) | V1—C4—H4 | 121.4 |
C3—V1—C6 | 159.67 (9) | C1—C5—C4 | 107.3 (2) |
C8—V1—C6 | 59.51 (8) | C1—C5—V1 | 72.69 (12) |
C4—V1—C6 | 124.39 (9) | C4—C5—V1 | 71.69 (12) |
N1—V1—C5 | 105.89 (8) | C1—C5—H5 | 126.3 |
C7—V1—C5 | 137.37 (8) | C4—C5—H5 | 126.3 |
C2—V1—C5 | 59.47 (8) | V1—C5—H5 | 121.1 |
C3—V1—C5 | 59.46 (9) | C10—C6—C7 | 108.56 (19) |
C8—V1—C5 | 121.96 (8) | C10—C6—V1 | 72.76 (11) |
C4—V1—C5 | 35.88 (9) | C7—C6—V1 | 70.79 (11) |
C6—V1—C5 | 105.71 (8) | C10—C6—H6 | 125.7 |
N1—V1—C1 | 76.87 (7) | C7—C6—H6 | 125.7 |
C7—V1—C1 | 152.37 (8) | V1—C6—H6 | 122.4 |
C2—V1—C1 | 35.55 (8) | C6—C7—C8 | 107.8 (2) |
C3—V1—C1 | 59.09 (8) | C6—C7—V1 | 73.41 (12) |
C8—V1—C1 | 157.20 (8) | C8—C7—V1 | 72.74 (12) |
C4—V1—C1 | 58.96 (8) | C6—C7—H7 | 126.1 |
C6—V1—C1 | 118.05 (8) | C8—C7—H7 | 126.1 |
C5—V1—C1 | 35.24 (7) | V1—C7—H7 | 119.6 |
N1—V1—C9 | 136.25 (7) | C9—C8—C7 | 107.7 (2) |
C7—V1—C9 | 59.34 (8) | C9—C8—V1 | 73.22 (12) |
C2—V1—C9 | 136.22 (8) | C7—C8—V1 | 71.11 (12) |
C3—V1—C9 | 104.17 (9) | C9—C8—H8 | 126.1 |
C8—V1—C9 | 35.25 (8) | C7—C8—H8 | 126.1 |
C4—V1—C9 | 76.87 (8) | V1—C8—H8 | 121.3 |
C6—V1—C9 | 58.91 (8) | C8—C9—C10 | 108.70 (19) |
C5—V1—C9 | 87.32 (8) | C8—C9—V1 | 71.53 (11) |
C1—V1—C9 | 122.30 (8) | C10—C9—V1 | 72.22 (12) |
N1—V1—C10 | 105.48 (7) | C8—C9—H9 | 125.7 |
C7—V1—C10 | 59.62 (8) | C10—C9—H9 | 125.7 |
C2—V1—C10 | 136.99 (8) | V1—C9—H9 | 122.3 |
C3—V1—C10 | 124.35 (9) | C6—C10—C9 | 107.2 (2) |
C8—V1—C10 | 59.52 (8) | C6—C10—V1 | 71.91 (11) |
C4—V1—C10 | 89.15 (9) | C9—C10—V1 | 72.06 (11) |
C6—V1—C10 | 35.33 (8) | C6—C10—H10 | 126.4 |
C5—V1—C10 | 77.77 (8) | C9—C10—H10 | 126.4 |
C1—V1—C10 | 104.44 (8) | V1—C10—H10 | 121.4 |
C9—V1—C10 | 35.72 (8) | C11—N1—V1 | 178.70 (17) |
N1—V1—Cl1 | 85.17 (5) | N1—C11—C12 | 179.2 (2) |
C7—V1—Cl1 | 81.68 (6) | C11—C12—H12D | 109.5 |
C2—V1—Cl1 | 83.62 (6) | C11—C12—H12E | 109.5 |
C3—V1—Cl1 | 80.40 (7) | C11—C12—H12F | 109.5 |
C8—V1—Cl1 | 80.17 (6) | C11—C12—H12A | 109.5 |
C4—V1—Cl1 | 111.40 (7) | C11—C12—H12B | 109.5 |
C6—V1—Cl1 | 115.25 (6) | H12A—C12—H12B | 109.5 |
C5—V1—Cl1 | 139.02 (6) | C11—C12—H12C | 109.5 |
C1—V1—Cl1 | 117.38 (6) | H12A—C12—H12C | 109.5 |
C9—V1—Cl1 | 111.99 (6) | H12B—C12—H12C | 109.5 |
C10—V1—Cl1 | 138.18 (6) | Cl5—Fe1—Cl2 | 109.26 (3) |
C5—C1—C2 | 108.6 (2) | Cl5—Fe1—Cl3 | 109.98 (3) |
C5—C1—V1 | 72.07 (12) | Cl2—Fe1—Cl3 | 107.67 (2) |
C2—C1—V1 | 70.84 (11) | Cl5—Fe1—Cl4 | 109.70 (3) |
C5—C1—H1 | 125.7 | Cl2—Fe1—Cl4 | 108.79 (2) |
C2—C1—H1 | 125.7 | Cl3—Fe1—Cl4 | 111.38 (3) |
Selected geometric parameters (Å, °). topCg1—V1 | 1.956 (1) | Cg1—V1—Cg2 | 134.10 (4) |
Cg2—V1 | 1.958 (1) | Cl1—V1—N1 | 85.17 (4) |
V1—N1 | 2.087 (2) | N1—C11 | 1.138 (3) |
V1—Cl1 | 2.369 (1) | C11—C12 | 1.451 (3) |
| | V1—N1—C11 | 178.7 (2) |
Cg1 is the centroid of atoms C1–C5 and Cg2 is the centroid of atoms C6–C10 |